Processing for silver halide color photographic materials comprises three basic steps including developing (in the case of the development for color reversal materials, a black-and-white (or first) development is employed before color development), desilvering, and washing. The desilvering step is composed of a bleach step and a fixing step or a monobath bleach-fixing ("blix") step which includes both bleaching and fixing.
In addition to the aforesaid steps, additional processing steps can be used, such as a stabilizing step, a prebath processing step before each processing step and a stop-bath processing step can be employed as is determined to be most suitable.
During color development, exposed silver halides present in imagewise exposed photographic material are reduced by a color developing agent to form silver and halide ions, and the resulting oxidized color developing agent simultaneously reacts with color couplers to form dyes. Accordingly, when many silver halide color photographic materials are continuously processed using an automatic processor or other continuous processing equipment, halide ions accumulate in the developer, thus rendering the developer unsuitable for further use.
Recently, in order to save natural resources and to help reduce environmental pollution, attempts have been made to reduce the amount of replenishers used with developers and other photographic processing solutions. However, an attempted resolution to this problem, e.g., by simply reducing the amount of replenisher used in a developer, encounters problems such as reduction in the developing activity of the developer due to the accumulation of other materials that dissolve out of photographic light-sensitive materials during processing. Such materials can include accumulated iodide and bromide ions, which are particularly strong development inhibitors, whose presence results in longer and unpredictable development times.
As another possible solution to the problem of excessive use of replenisher, there is a method of using less developer replenisher by increasing the pH and the processing temperature of the developer. However, such a method suffers from the problem that the photographic performance is highly variable during continuous processing and, additionally, the stability of the developer is reduced.
Also, another method for decreasing development times by reducing the accumulation of iodide ions or bromide ions utilizes a silver halide photographic material having a high silver chloride content, e.g., as disclosed in JP-A-58-95345, JP-A-59-232342 and JP-A-61-70552 (the term "JP-A" as used herein refers to a "published unexamined Japanese patent application") and WO 87-04534, and this method is considered to be an effective means of enabling fast processing with low amounts of replenisher used with the developer.
However, the aforesaid method suffers from the problem of difficulty in attaining very fast processing times (e.g., within 30 seconds) while maintaining stable color development and ensuring stable photographic developing during continuous processing using conventional color developing agents, such as, e.g., 4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethylaniline salt. In particular, it has been found that when silver halide photographic materials (e.g., having a high silver chloride content) are processed at high pH or a high processing temperature, the processing speed can be increased, but the resulting stability of both the processing solution and that of the developed photographic material are so reduced as to render this method of processing unsuitable for any practical or commercial use.
Additionally, JP-A-61-261740 and JP-A-61-275837 disclose the use of N-hydroxyalkyl-substituted p-phenylenediamine derivatives as a color developing agent, in order to inhibit undesirable variation in the photographic performance, due to the presence of accumulated bromide ion, when silver halide photographic materials are developed that comprise silver halides having mostly silver chlorobromide. The specifications cited above describe improvement of storage stability of formed color images by carrying out the color development in a short time in order to reduce the amount of the color developing agent remaining in the silver halide photographic materials.
Also, it is said that in the case of using a hydroxyalkyl-substituted p-phenylenediamine derivative, used as a color developing agent for developing color photographic papers, the storage stability, and in particular, the fastness to light of the color images obtained is greatly reduced. But it has been found that when a color photographic light-sensitive material (paper) having a silver halide emulsion layers containing at least 80 mol % silver chloride is processed by a color developer containing a 4-amino-3-methyl-N-ethyl-N-.beta.-hydroxyethylaniline salt, which is used as a color developing agent for conventional color photographic negative films and not containing benzyl alcohol, color images are formed fast (within 30 seconds) and the processing stability is excellent.
However, this method suffers from the problem that the fastness of the color images is greatly inferior to the case of using a 4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethylaniline salt in spite of processing in a short period of time. British Patent 807,899 discloses that the use of certain N-hydroxyalkyl substituted p-phenylenediamine derivatives provides excellent storage stability of cyan color images. However, with a conventional processing time containing a long color developing time, the storage stability of yellow color images and magenta color images are poor and the stored images greatly deteriorated the color balance and could not be worthy of appreciation.
The storage stability of color images is generally an important factor for print materials such as color paper, and hence 4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethylaniline salts have been used as the best compound.
At present, it has been a long-standing problem in this art to provide a commercially or practically suitable process that can reduce the amount of replenishers needed and, at the same time, reduce the processing and/or development time. However, as described above, previous attempts to provide such a process have failed, due to the occurrence of undesirable additional problems, including, e.g., reduced storage stability and reduced light fastness of color images formed on a developed photographic material.
For example, since the color images of developed photographic materials formed, using the aforesaid 4-amino-3-methyl-N-ethyl-N-.beta.-hydroxyethylaniline salt (which is a color developing agent for developing color photographic negative films), at present are greatly reduced, the aforesaid color developing agent is practically unsuitable for developing color photographic papers.
In general, the rate of color development varies according to which type p-phenylenediamine derivative is used as a component of the developing agent. For example, a color developing agent having a hydrophobic group at the N-substituted position, such as a 4-amino-3-methyl-N,N-diethylaniline salt and a 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline salt, is readily distributed with a coupler or other developer components into an oil drop phase of a photographic material, in order to increase the rate of developing reactions. Thus, such a color developing agent has been used for faster development. Examples of such developing agents and how they are made are disclosed in U.S. Pat. Nos. 3,656,905, 3,656,925 and 4,035,188.
Alternatively, a fast method of color development has been employed using a color developing agent having a hydrophilic group at the N-substituted position, such as a 4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethylaniline salt and a 4-amino-3-methyl-N-ethyl-N-.beta.-hydroxyethylaniline salt. Such a developer additionally contains benzyl alcohol, in order to accelerate the distribution of the color developing agent in the oil drop phases of a color photographic light-sensitive material.
However, such a method (using a hydrophobic group-containing agent, as described above) has the problem that when a color photographic material is color developed for a period of time of about 30 seconds or less, an insufficient contact of the developing agent with the lower emulsion layers of the color photographic material is effected, thereby producing developed color images having inferior color balance. Additionally, the presence of benzyl alcohol in the color developer may increase the coloring density in the uppermost emulsion layer but have little or no effect on the coloring density of the lowermost emulsion layer, thereby additionally causing poor or nonuniform color images on the developed photographic material and, hence, the addition of benzyl alcohol is not desired.